EP4149581A1 - Verfahren und vorrichtung zur herstellung eines faserverstärkten artikels - Google Patents
Verfahren und vorrichtung zur herstellung eines faserverstärkten artikelsInfo
- Publication number
- EP4149581A1 EP4149581A1 EP20816962.3A EP20816962A EP4149581A1 EP 4149581 A1 EP4149581 A1 EP 4149581A1 EP 20816962 A EP20816962 A EP 20816962A EP 4149581 A1 EP4149581 A1 EP 4149581A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- preform
- mold cavity
- fiber reinforced
- forming
- reinforced article
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
- B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods
- A61B17/56—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor
- A61B17/58—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor for osteosynthesis, e.g. bone plates, screws or setting implements
- A61B17/68—Internal fixation devices, including fasteners and spinal fixators, even if a part thereof projects from the skin
- A61B17/84—Fasteners therefor or fasteners being internal fixation devices
- A61B17/86—Pins or screws or threaded wires; nuts therefor
- A61B17/866—Material or manufacture
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L31/125—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L31/129—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix containing macromolecular fillers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
- B29C43/027—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles having an axis of symmetry
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/34—Feeding the material to the mould or the compression means
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/36—Moulds for making articles of definite length, i.e. discrete articles
- B29C43/3607—Moulds for making articles of definite length, i.e. discrete articles with sealing means or the like
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/36—Moulds for making articles of definite length, i.e. discrete articles
- B29C43/361—Moulds for making articles of definite length, i.e. discrete articles with pressing members independently movable of the parts for opening or closing the mould, e.g. movable pistons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0005—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor using fibre reinforcements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0053—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor combined with a final operation, e.g. shaping
- B29C45/0055—Shaping
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
- B29C45/14778—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the article consisting of a material with particular properties, e.g. porous, brittle
- B29C45/14786—Fibrous material or fibre containing material, e.g. fibre mats or fibre reinforced material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/26—Moulds
- B29C45/2618—Moulds having screw-threaded mould walls
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/26—Moulds
- B29C45/33—Moulds having transversely, e.g. radially, movable mould parts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/46—Means for plasticising or homogenising the moulding material or forcing it into the mould
- B29C45/56—Means for plasticising or homogenising the moulding material or forcing it into the mould using mould parts movable during or after injection, e.g. injection-compression moulding
- B29C45/561—Injection-compression moulding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
- B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
- B29C70/12—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of short length, e.g. in the form of a mat
- B29C70/14—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of short length, e.g. in the form of a mat oriented
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
- B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
- B29C70/462—Moulding structures having an axis of symmetry or at least one channel, e.g. tubular structures, frames
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B30—PRESSES
- B30B—PRESSES IN GENERAL
- B30B15/00—Details of, or accessories for, presses; Auxiliary measures in connection with pressing
- B30B15/02—Dies; Inserts therefor; Mounting thereof; Moulds
- B30B15/022—Moulds for compacting material in powder, granular of pasta form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B30—PRESSES
- B30B—PRESSES IN GENERAL
- B30B7/00—Presses characterised by a particular arrangement of the pressing members
- B30B7/04—Presses characterised by a particular arrangement of the pressing members wherein pressing is effected in different directions simultaneously or in turn
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods
- A61B2017/00526—Methods of manufacturing
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods
- A61B2017/00831—Material properties
- A61B2017/00964—Material properties composite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B11/00—Making preforms
- B29B11/14—Making preforms characterised by structure or composition
- B29B11/16—Making preforms characterised by structure or composition comprising fillers or reinforcement
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
- B29C43/021—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles characterised by the shape of the surface
- B29C2043/023—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles characterised by the shape of the surface having a plurality of grooves
- B29C2043/024—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles characterised by the shape of the surface having a plurality of grooves forming a threaded surface
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
- B29C43/027—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles having an axis of symmetry
- B29C2043/028—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles having an axis of symmetry using radial compression
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
- B29C43/027—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles having an axis of symmetry
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
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- B29C43/32—Component parts, details or accessories; Auxiliary operations
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- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/68—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks
- B29C70/84—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks by moulding material on preformed parts to be joined
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles
- B29K2105/14—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles oriented
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/25—Solid
- B29K2105/253—Preform
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2001/00—Articles provided with screw threads
- B29L2001/007—Screws
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/753—Medical equipment; Accessories therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/753—Medical equipment; Accessories therefor
- B29L2031/7532—Artificial members, protheses
Definitions
- the present invention relates to an apparatus and a method of manu- facturing a fiber reinforced article, and more particularly to a fiber reinforced arti- cle having a tailored multidirectional fiber orientation.
- Composite materials also referred to as composites, are a combination of two or more materials that are mixed or joined on a macroscopic level. They are used in engineering applications where a pure material cannot provide the specific set of properties that are required. They can be thought of as a single material that has been enhanced by the addition of another material.
- Fibers are added as a means of reinforcement and provide strength, stiffness, or any other desired property to the composite.
- One of the problems as- sociated with the above arrangement is how to preserve the desired multidirec- tional fiber orientation of a complex-shaped article during the manufacturing phase.
- An object of the present invention is thus to provide a method to solve the above problems related to manufacturing the articles with desired fiber orien- tations.
- the desired fiber orientation may be just a simple uniaxial orientation or complex multilayer multidirectional orientation depending on the end product re- quirements.
- the objects of the invention are achieved by a method and an appa- ratus which are characterized by what is stated in the independent claims.
- the pre- ferred embodiments of the invention are disclosed in the dependent claims.
- the invention is based on the idea of using radial molding and forming a fiber reinforced article, which comprises a tailored fiber orientation, from the mold cavity, wherein the continuous reinforcing fibers follow to a surface design of said article.
- Figure 1 is a flow chart of a method according to an embodiment
- Figures 2 and 3 illustrate exemplary die segments
- Figure 4 illustrates an exemplary composite preform
- Figures 5a-5f illustrate a series of exemplary manufacturing steps with pistons
- Figure 6 illustrates an alternative step of the exemplary manufacturing step.
- This invention is focused on fiber reinforced thermoplastic polymer composites, which can be especially used in medical devices such as bone screws and fasteners.
- Said medical devices are usually made of stainless steel or titanium alloys.
- these materials tend to have certain challenges, such as mechani- cal mismatch with mechanical properties of bone tissue which may cause further challenges such as stress shielding.
- Metallic implant may also cause disturbance in imaging such as in MR1. This has led engineers to search for alternative materials which can meet the desired effects and properties.
- Fiber reinforced polymer composite is composed of a combination of reinforcing fibers, and a ther- moplastic polymer matrix material, that surrounds the fibers. Fibers add strength and stiffness to an otherwise viscoelastic polymer that, without reinforcement, lacks the mechanical properties needed in certain applications. Fibers and matrix work together in synergy providing a composite material with characteristic prop- erties benefiting from the contribution of both elements.
- Fibers are added as a means of reinforcement and provide strength, stiffness, or any other desired property to the composite.
- the matrix bonds the fi- bers together, protects the fibers from damage, and distributes the load from one fiber to another.
- the properties of the composite are determined by the properties of the fibers, their length, diameter, orientation, and amount, as well as the proper- ties of the matrix, and the bonding between the matrix and the fibers.
- the fibers can be chopped and/or continuous.
- the continuous fibers When the continuous fibers are aligned, they provide maximum strength along the direction of alignment.
- the composite can be considerably weaker along other directions and can therefore be highly anisotropic.
- This anisot- ropy can be overcome by fibers aligned in desired directions, i.e. fiber orientations.
- One of the problems associated with the above arrangement is how to preserve the desired fiber orientation of a complex-shaped article during the man- ufacturing phase. On laminated planar structures this can be easily overcome by aligning fibers on desired fiber orientations on distinct layers or by selecting pre- manufactured sheets with desired fiber orientations. If the fiber reinforced article being manufactured is a simple rotationally symmetrical object the desired fiber orientation can be achieved by means of filament winding.
- the desired fiber orientation may be manufactured by means of automatic composite manufacturing techniques, such as automatic tape placement and/or automatic fiber placement. If, however, the complex fiber orientation is to be man- ufactured on small size products which need to be mass produced on large quantity on industrial scale, the preferable manufacturing techniques include compression molding and injection molding.
- the fiber orientation of a preform changes or it is considerably challenging to preserve on certain geome- try articles.
- Preserving the desired fibre orientation on planar structures is some- what straightforward, but more complex geometries are not that easy to reproduce with predictable fibre orientation.
- the shape transformation of a preform is not uniform along the surfaces of the object when compressing the preform to mold defining the final shape of the article.
- the desired fiber orientation of the article being manufactured can be achieved by using an insert containing the fibers having de- sired fiber orientation.
- the insert is placed inside the mold defining the final shape of the article before injecting the matrix polymer which fills the mold.
- the largest outer dimensions of the insert need to be smaller than the smallest outer dimen- sions of the mold, because otherwise the fiber insert would squeeze on between the mold parts when the mold closes making the injection molding impossible.
- the present invention relates to a continuous fiber reinforced structure forming method, which utilizes radial molding. Continuous fiber reinforced struc- ture obtained by this method for certain product geometries can comprise a layer structure with defined fiber orientation on each layer which can be tailored having desired properties.
- the construction/structure of desired fiber orientation of final product can be tai- lored/predicted as the shape transformation during the mold closing is uniform radially surrounding the longest dimension of the preform.
- the fiber orien- tation structure can even remain unchanged in the finished product, which maxim- izes benefits of the desired properties.
- Such properties can be, for example, tough- ness, stiffness, or any other desired mechanical property.
- Figure 1 illustrates a flow chart of a method of forming a fiber reinforced article according to an embodiment.
- the first step 101 comprises providing a com- posite preform composed of thermoplastic polymer matrix and reinforcing fibers, wherein the preform comprises an initial volume and initial fiber orientation.
- the preform may be rotationally symmetrical and comprise an intermingled or inter- locked layer structure, which would be preserved in the finished article.
- the pre- form may also comprise a tailored fiber structure, on which the fibers are initially located in separate and superimposed layers, and on which there are designed gaps on fiber structure on undermost layers and extra fibers on layers above the layers having gaps. These extra fibers on topmost layers may be located on the same po- sition as the gaps on undermost layers.
- each layer may consist of same or different material, and additionally may comprise a helix orientation having a desired angle such as 90°, 45° or 30°, for instance.
- the preform may con- sist of a core or insert wrapped around multiple layers having different helix, uni- axial, etc. orientation. In some structures, there may be gaps between different lay- ers which would further facilitate interlocking the fibers in the finished article.
- thermoplastic materials are materials which shape can be trans- formed when heating them to certain material specific temperatures (e.g. glass transition temperature, melting temperature, etc.). Certain material properties, such as degree of crystallinity, strength properties, etc., of thermoplastic polymers may also be altered as a function of temperature and time.
- glass transition temperature Tg glass transition temperature
- Semi-crystalline and crystalline thermoplastic polymers melt when they are heated to their melting point (Tm) or above melting point.
- Tm melting point
- Amorphous thermoplastic polymers do not have a melting point.
- thermoplastic polymers are molded on temperatures above the Tg or above the Tm. They solidify to a glassy state when cooled below their glass transition tem- perature.
- Fibers There are many different types of fibers that can be used to reinforce pol- ymer matrix composites. The most common are carbon fibers (AS4, 1M7, etc.) and fiberglass (S-glass, E-glass, etc.). Fibre preforms are often manufactured in sheets, continuous mats, tubular structures or as continuous filaments or continuous fila- ments/tapes impregnated using matrix polymer.
- the second step 102 comprises loading the preform inside a radial molding apparatus, either manually or automatically by a machine.
- Said radial molding apparatus comprises at least three adjacent die segments next to each other forming a mold cavity having an initial volume in an initial position and a final volume in a compressed position, which is smaller than the initial volume.
- the final volume of the mold cavity also defines a final volume and shape of the finished fiber reinforced article.
- Each die segment can be identical, such as wedge-shaped with planar surfaces, which are arranged to form an approximately cylindrical central cavity. However, other shapes can also be formed depending on the design of the cavity surface.
- the wedges can be hinged and driven in unison to change the diameter, and consequently the volume, of the cavity.
- the die segment can have any design comprising two adjacent sides forming a 120° or less angle.
- the third step 103 comprises molding the preform by moving said die segments.
- Each die segment is in direct contact with each other during end posi- tions and movement of the mold, such as opening and closing as well as during the initial and compressed position.
- the compression applies similar or identical radial force and deformation towards the longitudinal axis of the pre- form.
- Radial molding is a technique where the molded article is formed by a moldable continuous fiber reinforced preform material from the initial volume to the final volume along a plurality of radial directions. These radial directions are substantially perpendicular to a common longitudinal axis and arranged to lie in different planes.
- the common longitudinal axis refers to the axis along which preform is loaded and perpendicular to the compression.
- the said movable radial die segments are movable concurrently be- tween the initial position and the final compression position which respectively define said initial volume and said final volume.
- the volume of the mold cavity in the compressed position can be smaller than or equal to the volume of the preform. Additionally, the volume of the preform can be smaller than the volume of the mold cavity in the initial position, and transverse dimension of the preform in the initial position can be larger than the transverse dimension of finished article in the com- pressed position.
- the transverse dimension of the preform in the initial position can also be smaller than or equal to the transverse dimension of the finished article in the compressed position, wherein the preform is additionally compressed from an end along the common longitudinal axis of the preform.
- Linear or curved path actuators can be used to move said die segments between their initial and compressed positions.
- the said radial die segments can move along either linear or curved paths during which the interface surfaces on between the adjacent radial die segments can be then either linear or curved.
- the radial mold comprised of at least three mold die segments de- scribed in this invention may also be used as a mold for injection molding.
- injec- tion molding the mold which opens radially, as described in this invention, enables to use continuous fiber inserts which have even larger initial diameter than the molded final product.
- conventional mold there are always gaps on between the mold parts, also known as dies, when the mold opens and thus the use of such larger diameter inserts would be impossible, as the insert would get squeezed be- tween the mold parts when the mold closes. If the mold opens and closes radially as explained in this invention such squeezing will not happen. This enables to use such continuous fiber reinforced inserts in overmolding injection molding which are impossible to use when using any other type of molds in injection molding.
- the fourth step 104 comprises opening the mold cavity, by returning the die segments to the initial position, wherein each die segment is in direct con- tact with adjacent die segments during the movement.
- Both compression and re- lease movements can be actuated by actuators to forcedly move said die segments between their initial and compressed positions.
- Said actuator can be hydraulic power cylinder, for instance, attached to the die segments. Operation of the die seg- ments can be controlled by a valve.
- the power cylinders can be simultaneously connected to compress and, after compression, to reverse flow through the valve.
- the fifth step 105 comprises removing the obtained fiber reinforced ar- ticle from the mold cavity, either manually or automatically by a machine.
- the fin- ished article comprises a tailored orientation and layer structure, wherein the con- tinuous reinforced fibers follow or conform to a surface contour of said article.
- the initial fiber orientation structure can even remain unchanged in the finished article, which maximizes benefits of the desired properties.
- the obtained article comprises desired properties such as better toughness, as well as compression, torsion, im- pact resistance, or any other desired property.
- the method further comprises a heating step, wherein the preform is heated to above the glass transition temperature or melting temperature of matrix polymer. Heating the preform facilitates formability of the preform.
- Said heating step can be arranged inside the radial molding apparatus be- fore the molding step or before loading the preform inside the radial molding ap- paratus.
- the die segments can be heated using heating ele- ments placed inside the desired locations in the compression die body and transfer the heat to the preform located in mold cavity. The preform is then cooled down inside the mold cavity by conduction or the finished article is cooled down after the molding step by any suitable cooling means such as air cooling.
- the method before or after or during the molding step, further comprises sliding at least one piston inside the mold cavity along the common longitudinal axis of the preform to further facilitate the com- pression of the preform by sealing the mold cavity from at least one end.
- the piston refers to any rod or stick or similar arranged to fit and move inside the molding apparatus.
- one piston on each longitudinal end of the mold cavity can be provided, and during molding step, said pistons slide to- wards the preform and thus further compresses the preform from both ends.
- the pistons slide towards the preform after the die segments are moved to final compression position.
- a separate actuator may move the piston or both pistons.
- the piston may comprise a feature penetrating the whole mold cavity from one piston to another piston. Such embodiment is beneficial particu- larly when molding parts which have hollow opening trough the longest dimension of part. An example of such part is a cannulated screw.
- a distal end of the piston may comprise a mold with an inverse design which is reproduced at an end portion of the obtained fiber reinforced article.
- the mold can be made of plastic such as polyetheretherketone (PEEK), which has ex- cellent mechanical and chemical resistance properties that are maintained at high temperatures.
- PEEK polyetheretherketone
- the distal end in this context refers to the end contacting the pre- form.
- the design can be for instance a screw head and/or screw tip.
- the piston can include a separate part which is used as an insert and which is joined to the part being manufactured during the radial molding phase. Such insert is temporarily attached to piston prior to compression molding phase and it is permanently attached to the part being radial molded during the molding phase.
- Such insert may be composed of same material as part being manufactured or it may be composed of different material such as a metal, ceramic, etc.
- Such in- sert may comprise the whole tip of the part being manufactured. Such tip can be for instance threaded and used in applications where a mixture of two or more ma- terials is more advantageous.
- the preform is provided in a continuous manner by loading and compressing the preform, returning the die segments and removing the obtained fiber reinforced article in such way that the preform is moved equally or less than the length of the mold cavity in the direction of the com- mon longitudinal axis without separating the preform and the obtained fiber rein- forced article from each other.
- the loading can be performed automatically or man- ually.
- the actuator may move the preform to mold cavity on con- tinuous manner explained below:
- the outcome is a continuous radially molded article having desired fi- ber orientation and shape.
- the method fur- ther comprises sliding at least one piston with specifically designed mold sealing feature at the distal end of the piston along the common longitudinal axis of the preform to further facilitate mold sealing.
- the sealing feature stops at the edge of the mold cavity.
- the piston includes a geometrical feature which seals the mold at the stage where mold cavity is “open” (figure 2] before the die segments move to the compressed position (figure 3).
- the separate actuator may move the piston or both pistons.
- Figures 2 and 3 illustrate exemplary die segments 2 of a radial molding apparatus viewed along a longitudinal axis in an initial position and a compressed position, respectively.
- the apparatus comprises four die segments 2 forming a mold cavity 3.
- the die segments 2 can be similar or different depending on the manufactured product.
- Each die segment 2 comprises two inter- face surfaces 2a forming a wedge, which are in contact with interface surfaces 2a of adjacent die segments 2 all the time during an initial position (Fig. 2), molding step and compressed position (Fig. 3) and during movements between the posi- tions.
- the die segments 2 can move along linear path which the interface surfaces 2a between the adjacent die segments 2 can be linear.
- Figure 4 illustrates an exemplary composite preform 1 comprising ther- moplastic polymer matrix and reinforcing fibers.
- the preform 1 comprises a core 11 having uniaxial fiber orientation and plurality surrounding fiber layers 12 hav- ing a substantially 45° helix orientation.
- the helix orientation may be either or both right hand or/and left hand.
- the layers 12 maybe overlapped with 45°/-45°/45°/- 45°/45° etc. helix orientation, for example.
- the layers 12 may overlap with differ- ent or same helix orientation from the core 11 to the surface, wherein the fibers of the core 11 comprise same orientation parallel to the longitudinal axis.
- the layers 12 may have same helix orientation close to the core 11 and different helix orientation close to the surface.
- the continuous reinforcing fibers are arranged to follow or conform to a surface design of finished article.
- the helix angle is essential for determining torque. Screw efficiency is controlled by the helix angle, and the maximum efficiency is between 40 and 45 degrees.
- the helix orientation can be substantially 15° or 30° or parallel to the longitudinal axis.
- the fiber insert 11 may also be re- placed with a different material.
- Figures 5a-5f illustrate a series of exemplary manufacturing steps com- prising similar die segments from Figures 2 and 3 with pistons 4, 5 in open views, wherein two front adjacent die segments 2 are not shown.
- Figure 5a illustrates the die segments 2 in the initial position, wherein a mold cavity 3 has an initial volume.
- the mold cavity 3 in this example has a shape of a threaded screw.
- Figure 5b illustrates the die segments 2 and pistons 4, 5 in initial posi- tions, wherein a preform 1, having an initial shape and volume and comprising thermoplastic polymer matrix and reinforcing fibers, has been loaded inside the mold cavity 3.
- the preform 1 has a common longitudinal axis A which is perpen- dicular to compression.
- the initial volume of the preform 1 can be smaller than the initial volume of the mold cavity 3, and in a compressed position the mold cavity 3 and a finished article has a matching volume.
- the first piston 4 and the second pis- ton 5 may have different diameter and shape but they may also have same diameter (as shown in Fig. 6).
- the pistons 4, 5 can be made of metal or metal with plastic tip such as PEEK.
- Figure 5c illustrates a step, wherein the die segments 2 are at the com- pressed position while the pistons 4, 5 are still at the initial position.
- longitudinal shape of the preform 1 is formed and having a tailored fiber orientation wherein the continuous reinforcing fibers follow or conform to the surface contour.
- both end sections have a protrusion with non-controlled shape (shown as round shape in Fig. 5c), which may not be a de- sired design.
- Figure 5d illustrates the complete compressed position, wherein both pistons 4, 5 have slid inside the mold cavity 3 after the radial compression.
- the volume of the mold cavity 3 in the compressed position equals to the volume of the finished article 6.
- the first piston 4, and/or the second piston 5, has a distal end, which is the end contacting the preform 1 or unfinished article, that functions as a mold with an inverse design which is reproduced at an end portion of the finished article 6.
- Figure 5e illustrates the step, where the die segments 2 and pistons 4 and 5 are returned to the initial position and the finished article 6 is ready to be removed.
- Figure 5f illustrates a closer view of the finished article 6, which can be divided into the end portion 6a, middle portion 6b and tip portion 6c.
- the end por- tion 6a has a top shape which is formed by the first piston 4.
- the middle portion 6b has the helix threads which have the tailored fiber orientation with optimized me- chanical properties.
- the tip portion 6c can be flat or, in some embodiments, include a tip made of other material than the preform 1. It may be fully threaded or partially threaded or smooth.
- Figure 6 illustrates an alternative step of the exemplary manufacturing steps.
- the embodiment of Figure 6 is very similar to the one explained in connec- tion with Figure 5c. Therefore, the embodiment of Figure 6 is in the following mainly explained by pointing out differences.
- Figure 6 illustrates a step before the radial compression, wherein the pistons 4, 5 are at the compressed position while the die segments 2 are still at the initial position (i.e. 5b).
- the pistons 4, 5 can either compress the end portion of the preform 1 to the desired design before radial compression or keep the preform 1 from flowing out of the mold cavity 3 during the radial compression while the ra- dial compression pressure causes the preform 1 to push towards the pistons 4, 5 or both.
- the piston 4, 5 may further comprise a sealing feature 7 at the interface of the mold cavity 3 along the common longitudi- nal axis A of the preform 1 to further facilitate mold sealing.
- the term “interface of the mold cavity 3” in this context refers to the border where the mold cavity 3 is defined by the final volume.
- the sealing feature 7 is shaped to seal the interface of at proximal and/or distal end of the mold cavity 3 when the die segments 2 are still at the initial position and arranged to focus and lock against rotation of the die seg- ments 2 at the compressed position.
- the sealing feature 7 When the sealing feature 7 is utilized, the diameter of the pistons 4, 5 may be smaller than the diameter of the mold cavity 3 in the compressed stage.
- the sealing feature 7 may be manufactured of any suitable sealant material such as rubber, metal or plas- tics such as PEEK.
- the sealing feature 7 may also be composed of same material as the rest of the pistons.
- the sealing feature 7 may also be a geometrical feature of the piston 4, 5, which is integrated or seamlessly joined to the piston 4, 5 and which is composed of any suitable material.
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Composite Materials (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Orthopedic Medicine & Surgery (AREA)
- Surgery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
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- Neurology (AREA)
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- Molecular Biology (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Moulding By Coating Moulds (AREA)
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Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL20816962.3T PL4149581T3 (pl) | 2020-11-30 | 2020-11-30 | Sposób wytwarzania wzmacnianych włóknami wyrobów i urządzenie |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/EP2020/083887 WO2022111826A1 (en) | 2020-11-30 | 2020-11-30 | Method for manufacturing fiber reinforced article and apparatus |
Publications (3)
| Publication Number | Publication Date |
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| EP4149581A1 true EP4149581A1 (de) | 2023-03-22 |
| EP4149581B1 EP4149581B1 (de) | 2024-03-27 |
| EP4149581C0 EP4149581C0 (de) | 2024-03-27 |
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| EP20816962.3A Active EP4149581B1 (de) | 2020-11-30 | 2020-11-30 | Verfahren und vorrichtung zur herstellung eines faserverstärkten artikels |
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| Country | Link |
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| US (1) | US20240001630A1 (de) |
| EP (1) | EP4149581B1 (de) |
| JP (1) | JP7588905B2 (de) |
| KR (1) | KR102888546B1 (de) |
| CN (1) | CN116600729B (de) |
| AU (1) | AU2020478278B2 (de) |
| ES (1) | ES2980574T3 (de) |
| IL (1) | IL303233B2 (de) |
| PL (1) | PL4149581T3 (de) |
| WO (1) | WO2022111826A1 (de) |
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| JP6659658B2 (ja) * | 2017-12-12 | 2020-03-04 | ハードロック工業株式会社 | 炭素繊維強化複合材料からなるネジ山を有するネジ筒の製造方法 |
| US12318124B2 (en) | 2021-11-29 | 2025-06-03 | Warsaw Orthopedic, Inc. | Continuous fiber bone screw and method of manufacture |
| DE102024110008A1 (de) * | 2024-04-10 | 2025-10-16 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Presswerkzeugvorrichtung zur Herstellung eines Längsbauteils aus einem Faserverbundwerkstoff und Verfahren |
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| JPS4944068A (de) * | 1972-09-02 | 1974-04-25 | ||
| IT1172879B (it) * | 1978-02-01 | 1987-06-18 | Fiat Spa | Procedimento e dispositivo per la compattazione di polveri, di granulati e di materiali sminuzzati |
| JPH0216040A (ja) * | 1988-07-04 | 1990-01-19 | Toray Ind Inc | 両歯付き無端ベルト成形用金型 |
| US5209888A (en) * | 1988-12-16 | 1993-05-11 | Fukuvi Chemical Industry Co., Ltd. | Method for producing frp screw-like fastening elements |
| US5529736A (en) * | 1994-08-10 | 1996-06-25 | Clemson University | Process of making a bone healing device |
| EP0795336B1 (de) * | 1995-09-14 | 2003-06-11 | Takiron Co. Ltd. | Osteosynthetisches material, verbundwerkstoff für implantate und verfahren zu ihrer herstellung |
| EP1506882B1 (de) * | 2003-08-11 | 2008-07-09 | Campagnolo Srl | Fahrradfelge aus Verbundwerkstoff und Verfahren zu ihrer Herstellung |
| FI120333B (fi) * | 2003-08-20 | 2009-09-30 | Bioretec Oy | Huokoinen lääketieteellinen väline ja menetelmä sen valmistamiseksi |
| US7128547B2 (en) * | 2004-01-13 | 2006-10-31 | Chien-Min Sung | High pressure split die and associated methods |
| CN1299654C (zh) * | 2004-06-24 | 2007-02-14 | 上海交通大学 | 全髋股骨头假体 |
| US8043553B1 (en) * | 2004-09-30 | 2011-10-25 | Advanced Cardiovascular Systems, Inc. | Controlled deformation of a polymer tube with a restraining surface in fabricating a medical article |
| EP1880379A4 (de) * | 2005-04-15 | 2011-08-31 | Mach Solutions Inc | Gesenkschmiedetechnologie |
| CA2680827C (en) * | 2007-03-22 | 2016-09-13 | P Tech, Llc | Methods and devices for intracorporeal bonding or interlocking of implants with thermal energy |
| FI125678B (fi) * | 2011-08-26 | 2016-01-15 | Bioretec Oy | Bioabsorboituva, orientoitu, muotoiltava kiinnitysmateriaali ja -levy |
| US20130218214A1 (en) * | 2012-01-16 | 2013-08-22 | Carbofix Orthopedics Ltd. | Bone screw head design |
| JP6408556B2 (ja) * | 2013-03-14 | 2018-10-17 | バイオ ディージー インコーポレイテッド | 向上した分解速度を有する生分解性合金を含む埋め込み型医療デバイス |
| DE102015102465B4 (de) * | 2015-02-20 | 2021-01-21 | Carbovation Gmbh | Verfahren zur Herstellung eines Felgenringes, Verfahren zur Befestigung von Speichen, Felge, insbesondere Drahtreifenfelge und Fahrrad |
| JP2017003091A (ja) | 2015-06-15 | 2017-01-05 | 三星産業貿易株式会社 | ねじ締結部品の製造方法 |
| US9821363B2 (en) | 2015-09-30 | 2017-11-21 | Ed Goff | Radial compression device with constrained dies |
| DE102015221168A1 (de) | 2015-10-29 | 2017-05-04 | Contitech Antriebssysteme Gmbh | Verfahren und Fertigungsvorrichtung zur Herstellung eines Doppelzahnriemens |
| WO2017139421A1 (en) * | 2016-02-08 | 2017-08-17 | Blockwise Engineering Llc | Radial compression apparatus and method of incrementally compressing an artcle using same |
| CN106620895B (zh) * | 2016-12-16 | 2019-12-31 | 厦门市豪尔新材料股份有限公司 | 一种碳纤维和聚醚醚酮复合接骨板及其制备方法 |
-
2020
- 2020-11-30 US US18/255,091 patent/US20240001630A1/en active Pending
- 2020-11-30 PL PL20816962.3T patent/PL4149581T3/pl unknown
- 2020-11-30 IL IL303233A patent/IL303233B2/en unknown
- 2020-11-30 JP JP2023532820A patent/JP7588905B2/ja active Active
- 2020-11-30 EP EP20816962.3A patent/EP4149581B1/de active Active
- 2020-11-30 ES ES20816962T patent/ES2980574T3/es active Active
- 2020-11-30 WO PCT/EP2020/083887 patent/WO2022111826A1/en not_active Ceased
- 2020-11-30 CN CN202080107444.9A patent/CN116600729B/zh active Active
- 2020-11-30 AU AU2020478278A patent/AU2020478278B2/en active Active
- 2020-11-30 KR KR1020237021351A patent/KR102888546B1/ko active Active
Also Published As
| Publication number | Publication date |
|---|---|
| EP4149581B1 (de) | 2024-03-27 |
| CN116600729B (zh) | 2025-03-21 |
| EP4149581C0 (de) | 2024-03-27 |
| JP2023551330A (ja) | 2023-12-07 |
| PL4149581T3 (pl) | 2024-08-12 |
| CN116600729A (zh) | 2023-08-15 |
| IL303233B1 (en) | 2024-10-01 |
| ES2980574T3 (es) | 2024-10-02 |
| WO2022111826A1 (en) | 2022-06-02 |
| AU2020478278B2 (en) | 2024-05-23 |
| KR20230112140A (ko) | 2023-07-26 |
| IL303233B2 (en) | 2025-02-01 |
| US20240001630A1 (en) | 2024-01-04 |
| AU2020478278A1 (en) | 2023-07-06 |
| JP7588905B2 (ja) | 2024-11-25 |
| KR102888546B1 (ko) | 2025-11-20 |
| IL303233A (en) | 2023-07-01 |
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